Dielectric coatings and use in capacitors

ABSTRACT

A coated substrate product is described comprising a substrate and a dielectric coating material comprising carbon, hydrogen, silicon, and oxygen. According to the method, the substrate is processed by plasma cleaning the surface and then depositing a dielectric coating by a suitable plasma process. The coating may contain one or more layers. The substrate may be a rigid material or a thin film or foil. The coated products of this invention have superior dielectric material properties and utility as substrates for the manufacture of rolled or parallel plate capacitors with high energy densities.

This application claims benefit to U.S. Provisional Application Ser. No.60/650,703 filed Feb. 7, 2005, the entire contents of which areincorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to a material and the process fordepositing coatings with superior dielectric properties to be used asdielectrics in rolled or parallel plate capacitors. More particularly,the invention relates to a process for applying coatings to films andfoils or parallel plates which can be energized to form capacitors forenergy storage.

2. Description of Related Art

Rolled capacitors are typically formed by alternating layers of metal(the electrodes) with layers of polymer dielectrics in a rolledgeometry. Parallel-plate capacitors can be manufactured in the same wayby alternating layers of rigid electrodes and polymer or ceramicdielectrics. Polymer dielectrics have limitations in temperaturestability, dielectric strength, and dissipation factors. For a givenvoltage rating, the required polymer thickness can be significant,typically greater than 2 micron. Ceramic dielectrics often suffer fromlow dielectric strengths.

Existing methods for using coatings on metal electrodes as thedielectrics in rolled and parallel-plate capacitors include, e.g.,traditional diamond-like carbon films (DLC's), which typically compriseamorphous carbon films which may or may not contain hydrogen, andtypically exhibit a mixture of sp3 (diamond-type) and sp2(graphite-type) chemical bonds, which have been proposed as a dielectriccoating material. The resultant deposition rates are often very slow,and hence, of no commercial value for this application.

Plasma deposition methods for the application of dielectric coatingssuffer from one or more of the following deficiencies and shortcomings:

(1) Difficulty in pre-cleaning of substrates prior to deposition;

(2) Poor adhesion of the dielectric layer;

(3) High permeation of the coatings by water vapor and oxygen andsubsequent degradation of dielectric properties;

(4) Fabrication of defect-laden or permeable, low density coatings;

(5) Poor control of coating properties during a deposition run;

(6) Poor coating thickness control and reproducibility of thickness;

(7) Coating stress is sufficient to cause wrinkling of the foil or filmsubstrate or electrode;

(8) Poor control of coating uniformity along a long length of substrate;

(9) Inability to scale-up the deposition process for mass production;and

(10) Brittle coatings which crack or craze during rolling processes.

Ion beam etching and deposition of many materials, including webs andfoils is known. Surface modification processes or thin film depositionprocesses by ion beams are routinely used for food packaging to decreasepermeability to oxygen and lengthen shelf lives of products.

Unfortunately, due to the high compressive stress it is difficult todeposit traditional DLCs on soft plastics and films and foils such aspolycarbonate or polyester to thicknesses greater than 0.1 micronswithout the formation of stress cracks or wrinkling of the substrate.DLC is therefore unsuitable as a thick (i.e. greater than 0.1 micronthick coating) on such substrates.

The following documents illustrate existing coating processes anddielectric coatings:

Kaganowicz, U.S. Pat. No. 4,168,330, describes a process for depositinga silicon dioxide layer on a substrate by activating a mixture of cyclicsiloxanes and oxygen “around the substrate by means of a glowdischarge.” It is taught that this plasma polymerization process wasdesigned for depositing thin dielectric layers on audio/video discs.

S. Fries-Carr, R. L. C. Wu and P. B. Kosel, U.S. Pat. No. 5,844,770,describes the use of dielectric coated materials in rolled capacitors

B. Knapp, F. Kimock, R. Petrmichl, N. Galvin, U.S. Pat. No. US RE37294describe the deposition of abrasion-resistant coatings using ion beamdeposition processes.

Petrmichl, R., Knapp, B., Kimock, F., Daniels, B., U.S. Pat. No.5,618,619 describes the material and composition of a Highly AbrasionResistant Flexible Coatings for Soft Substrates.

However, none of these documents disclose a method for producing adielectric coated substrate that has all of the properties necessary ordesirable for incorporation into a rolled capacitor, including highdielectric constant, high dielectric strength, high breakdown voltage,low dissipation factor, and is highly adherent and able to be rolled.Thus, there remains a need in the art for a method for producing such adielectric-coated substrate, as well as for the substrate itself andcapacitors produced therefrom.

SUMMARY OF THE INVENTION

The invention provides a material and an improved method for depositionof a dielectric coating onto substrates. More particularly, thisinvention provides a method for producing a dielectric-material coatingon the surface of a film, foil, or solid substrate which is highlyadherent, and exhibits high dielectric strength, high dielectricconstant, and low dissipation factor. Still more particularly, thisinvention provides a low cost and efficient process for mass-producingdielectric coatings on long lengths of substrates. The method isespecially useful for applying dielectrics to metal foils and metallizedpolymer films at high deposition rates, allowing them to be formed intorolled capacitors.

The product of the invention contains an amorphous, conformal,dielectric coating comprising the elements of C, Si, H, and O. Thecoatings may also contain N. The coatings are deposited from precursorgases containing at least the elements of which the coating iscomprised, in the presence of a plasma. The dielectric properties,stress, and chemistry of the coatings can be tailored to suit the needsof the particular substrate and performance requirements of the coatedproduct. These properties make the coatings of the present inventionideally suited to film and foil-type substrates for rolled capacitors.

One process method for deposition of these coatings uses an ion beamsource which operates with precursor gases comprising at least one ofthe following combinations of elements selected from the groupconsisting of Si and C; Si, C and H; Si and N; Si, N and H; Si and O;Si, O and H; Si, O and N; Si, C, H and O; Si, C, O and N; and Si, C, H,O and N. The process of the present invention is particularlywell-suited to the manufacture of dielectric coatings with tailoredhardness, stress, and chemistry. These properties make the coatings ofthe present invention ideally suited to application to plasticsubstrates, such as polymer films and metallized polymer films. Theresulting coatings are sufficiently adherent and flexible to allow thecoated substrates to be formed into a roll capacitor. Coatings whichhave properties resembling silicon carbide, silicon nitride, silicondioxide, and hydrogenated and oxygenated forms of these materials canalso be made by this process.

In the method of the invention, a chemically cleaned substrate (i.e., asubstrate that has been cleaned to remove unwanted materials and othercontaminants) is inserted into a vacuum chamber; which is pumped down toevacuate all or most of the air (e.g., to a vacuum of around 10⁻³ torr).The material is moved past one or more plasma ion sources which provideone or more beams of energetic ions to sputter-etch the substratesurface and assist in the removal of residual contaminants, such asresidual hydrocarbons and surface oxides, and which are believed toactivate the substrate surface to subsequent reaction with the depositedcoating.

After the substrate surface has been etched, a dielectric coatingcomprising C, H, Si, and O (and optionally N) is deposited by using adeposition flux containing C, H, Si, and O (and optionally N) onto thesurface of a fixed substrate or moving web of film or foil. Thedeposition flux is created by providing gaseous precursor compounds inthe presence of a plasma, which can be effectively generated by an ionbeam. The deposition conditions and substrate movement speed areadjusted to produce the desired properties in and thickness of thecoating. This (desirably plasma ion beam-) deposited coating may containone or more layers. Once the desired thickness of the coating has beenachieved, the deposition process on the substrates is terminated, thevacuum chamber pressure is increased to atmospheric pressure, and thecoated substrates, having superior dielectric properties, are removedfrom the vacuum chamber.

The coatings of the present invention may be capped with a top or outerlayer of another material to provide chemical resistance, barrierproperties and reduced surface friction.

In one embodiment, therefore, the invention relates to a method fordepositing onto a substrate a dielectric coating material containing oneor more of C, H, Si, and O, which comprises:

(a) mounting a substrate in a deposition vacuum chamber and placing thechamber under vacuum;

(b) etching the surface of the substrate with energetic ions, chemicallyreactive species, or a combination of these, thereby providing acleaned, activated surface;

(c) depositing onto the cleaned activated surface an layer of dielectricmaterial by exposing the substrate to a deposition flux oforgano-silicon or silane-based precursors which could includeorganosiloxanes, silanes, organosilazanes or mixtures thereof and alsomay include oxygen in the presence of a plasma; and

(d) recovering the substrate coated with a first dielectric layer.

In another embodiment, the invention relates to the coated substrateproduced by this method. More particularly, the invention relates to adielectric-coated substrate, comprising a first layer of dielectriccoating material comprising carbon, hydrogen, silicon, and oxygen.Desirably, this dielectric coating material has a dielectric strengthranging from about 200 V/μm to about 2400 V/μm and higher. Dielectriccoating materials having dielectric strengths greater than about 600V/μm are particularly suitable. The dielectric coating material caninclude those having dissipation factors less than about 2%.

In yet another embodiment, the invention relates to capacitorscomprising the coated substrate described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing breakdown voltage test results for a coatedsubstrate produced according to one embodiment of this invention.

FIG. 2 is a graph showing capacitance test results for a coatedsubstrate according to one embodiment of this invention.

FIG. 3 is a graph showing capacitance test results for a coatedsubstrate according to one embodiment of this invention.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

The product of the present invention substantially reduces or eliminatesthe disadvantages and shortcomings associated with the prior arttechniques by providing coatings with high dielectric strength, lowdissipation factor, high dielectric constant coating, and very adherentcoating by a manufacturing process which can be readily scaleable tolong lengths of materials suitable for device fabrication.

In a particular embodiment of this invention, mixtures of one or moreorganosiloxane, organosilane, or organosilazane precursor gases andoxygen are introduced into the vacuum chamber, and deposition conditionsare adjusted so that coatings with the combination of the followingelectrical physical properties are produced, which combination ofproperties are remarkable when compared to prior art coatings. Precursorgases comprising hexamethyldisiloxane, tetramethylcyclotetrasiloxane,octamethylcyclotetrasiloxane, or mixtures thereof have been found to besuitable in this regard.

These precursor gases are provided in the presence of a plasma, whichmay be generated by an ion beam. A gridless ion source, such as an EndHall ion source, Hall current ion source, or closed-drift ion source issuitable.

A particularly suitable method of demonstrating these principles is theuse of a gridless, closed-drift DIAMONEX® CD SOURCE (Morgan AdvancedCeramics, Inc.) for plasma ion beam processing in conjunction with aweb-handling system that is capable of continuously moving a film orfoil past the ion source while providing back-side cooling to thesubstrate. The dielectric material may also be produced by use of RFplasma processes by traditional parallel plate plasma reactors.

Important characteristics of the process include:

-   -   1. The ability to keep the internal compressive stress of the        coating low coupled with excellent adhesion allows the        deposition of thick coatings on a variety of substrate materials        and thicknesses. It is necessary to have coating thicknesses        greater than 0.1 micron in order to obtain sufficient dielectric        breakdown voltages.    -   2. Excellent adhesion of the dielectric layer(s) is produced by        generating an atomically clean surface prior to the deposition        of the coating. The coating is preferably deposited immediately        upon completion of the etching step to achieve maximum adhesion        to the substrate. Deposition of the coating layer(s) immediately        upon completion of the etching step minimizes the possibility        for recontamination of the etched surface with vacuum chamber        residual gases or other contaminants.    -   3. Overcoming the difficulties in obtaining an atomically clean        surface by sputter-etching the substrates using an ion beam of        controlled current and energy. It has been found that the        control of ion beam current and beam energy to within 1% is        consistently achieved which results in a highly repeatable and        predictable rate of removal of surface contaminant layers. In        addition, the ion beam sputter-etching process is conducted in        high vacuum conditions, such that oxidation or contamination of        the surface with residual gases in the coating system is        negligible. Finally, the apparatus geometry can be configured        such that the majority of sputtered contaminants deposit on the        vacuum chamber walls, and they do not re-deposit onto the        surface of the part as it is being sputter-etched.    -   4. Producing excellent adhesion of the dielectric ion beam        deposited layer(s) by generating an atomically clean surface        prior to the deposition of the coating. For most applications,        the deposited protective layer contains silicon, however,        multiple applications of different chemistries can be used to        form multiple different layers on the substrate. For        applications in which the topmost layer of the coating does not        contain silicon, adhesion can be enhanced via the use of        silicon-containing adhesion-promoting interlayers between the        top coating, e.g. DLC, and the substrate. In either case, the        ion beam deposited layer is preferably deposited immediately        upon completion of the ion beam sputter-etching step to achieve        maximum adhesion to the substrate. Deposition of the coating        layer(s) immediately upon completion of the ion beam        sputter-etching step minimizes the possibility for        re-contamination of the sputter-etched surface with vacuum        chamber residual gases or other contaminants. The        silicon-containing layers include a variety of amorphous        materials, such as silicon oxide, silicon nitride, silicon        oxy-nitride, silicon carbide, silicon oxy-carbide, silicon        carbonitride, the so-called silicon-doped DLC, mixtures thereof        and chemical combinations thereof. Each of the        silicon-containing interlayers may contain hydrogen.    -   5. Obtaining minimal batch-to-batch or “along the length”        variation in the properties of the coatings. This is the case        because process parameters such as ion energy, ion current        density, gas flow rate, and deposition chamber pressure are        largely decoupled in the ion beam deposition method of the        present invention, and because each of these process parameters        can be accurately controlled and reproduced to a high degree of        certainty, often to within 1%. In addition, the process endpoint        coating thickness is easily defined and reproduced.    -   6. Being readily scaled-up to accommodate mass production        because large scale ion beam sources are commercially available.        For example, commercially available ion beam sources in either        circular or linear geometries have been used for sputter        etching, surface modification, or deposition of coatings over        wide films and foils.

It is understood that the process of the present invention can becarried out in a batch-type vacuum deposition system with anincorporated web-handling system, in which the main vacuum chamber isevacuated and vented to atmosphere after processing each roll ofsubstrate material or inline processing vacuum deposition chambers, inwhich web or foil moves constantly from atmosphere, through differentialpumping zones and slit valves, into the deposition chamber, back throughdifferential pumping zones, and returned to atmospheric pressure. Theinvention is therefore suitable for depositing coatings to a widevariety of substrate materials, such as polymers, metals, glasses,ceramics, or combinations of these. For making the resulting coatedsubstrates into capacitors, a metallized polymer film, such as mylar, isparticularly suitable.

Additionally, to improve the deposition rate and throughput of thecoating machine, multiple ion sources can be utilized and operatedsimultaneously. Operation of the ion sources can be sequenced for thecase in which different coating materials are deposited from each ionsource. As described in U.S. Pat. No. 4,490,229, an additional ionsource can be used to co-bombard the substrates during coatingdeposition to alter the film properties.

In a particular method for depositing the coatings of the presentinvention, either multiple ion sources or multiple passes of thematerial past a single ion source are used to sequentially process along length of substrate material.

In the first step of the process, the substrate material is insertedinto a vacuum chamber, and the air in the chamber is evacuated. For thecase of ion beam deposition, typically, the vacuum chamber is evacuatedto a pressure of 1.0×10⁻⁵ Torr or less to ensure removal of water vaporand other contaminants from the vacuum system. However, the requiredlevel of vacuum which must be attained prior to initiating the next stepmust be determined by experimentation. The exact level of vacuum isdependent upon the nature of the substrate material, the sputter-etchingrate, the constituents present in the vacuum chamber residual gas, andthe details of the coating process. It is not desirable to evacuate tolower pressures than necessary, as this slows down the process andreduces the throughput of the coating system.

In the second step of the process, the substrate surface is bombarded byenergetic ions or exposed to reactive species to remove residualcontaminants, e.g. any residual hydrocarbons, surface oxides and otherunwanted materials not removed in the first step, and to activate thesurface. This etching of the substrate surface is required to achievehigh adhesion between the substrate surface and the coating layer(s).The etching can be carried out with inert gases such as argon, krypton,and xenon. Additionally, hydrogen or oxygen may be added to the inertgases or used independently to etch and activate the surface. Ionenergies as high as 2000 eV can be used, but ion energies less than 500eV result in the least amount of atomic scale damage to the substrate.

Immediately after the substrate surface has been etched, a coating layeris deposited on the substrate by a deposition flux which includesenergetic ions and contains the elements C, Si, H, O, and optionally N.The deposition flux is generated by introducing precursor gasescontaining the elements C, Si, H, O, and optionally N, into a plasma.These precursor gases may be blended with other inert gases, e.g. argon.The precursor gases undergo “activation” in the plasma or in the ionbeam itself. Examples of “activation” include, but are not limited tosimple electronic excitation, ionization, chemical reaction with otherspecies, ions and neutrals, which may be vibrationally or electronicallyexcited, and decomposition into simpler ionic or neutral species whichmay be vibrationally or electronically excited. Ions are extracted fromthe plasma or ion source and strike the surface to be coated withenergies from about 10 to about 1500 eV. The ion impact energy dependson the electric field between the point of origin of the ion and thesample, and the loss of energy due to collisions which occur between theion and other ionic or neutral species prior to the impingement of theion onto the substrate. Other activated species may also condense on thesubstrate surface. Neutral species will strike the surface with avariety of energies, from thermal energy to hundreds of eV, depending onthe origin of the neutral species. This highly energetic depositionprocess produces highly adherent, very dense and hard coatings on thesubstrate surface. The density, hardness and other properties of thecoating are all very dependent on the energetics of the depositionprocess as well as the precursor gases used.

In the ion beam process, the primary control parameters are theprecursor gas flow, the oxygen gas flow, the pumping speed, and the beamenergy and current density. The useful range of the latter is, however,limited for temperature sensitive substrates, such as polymers. Otherprocess parameters that affect the coating properties are the total flowrate, speed of the material as it passes the ion source(s) and thepresence of external magnetic fields.

The following describes several different forms of the plasma ion beamdeposited, dielectric coating. In the simplest case, the depositionprocess conditions are not changed between passes and a singledeposition pass is used, resulting in a single layer coating. Thethickness of this layer can be from about 0.1 micron (1000 Angstroms) toabout 3 microns (30,000 Angstroms), depending on the capacitor designrequired by the application. Generally, thicker coatings provide higherbreakdown voltages.

A variety of precursor gases and reactive gases for the deposition ofdielectric material layers have been investigated. Some examples of thegeneralized results are shown in TABLE 1

TABLE 1 Dielectric Reactive Resulting Precursor Formula gas Film GeneralResult TMS SiC4H12 SixCyHz electrical data erratic, reasonabledeposition rates Methane CH4 CyHz Poor adhesion, low deposition rateMethane CH4 CyHz High BDV but very low deposition rate (35-400 A/min)Methane CH4 H2 CyHz+ minimal improvement by H2 addition, low depositionrates TMS SiC4H12 O2 SixOyCzHa BDV >600 V/um TMS SiC4H12 H2 SixOyCzHa+Inconsistent properties, low BDV Cyclohexane C6H12 CyHz Rate higher thanmethane but inconsistent, low BDV OMCTS Si4O4C8H24 O2 SixOyCzHa Veryhigh rates, high BDV (>700 V/ um)

Deposition rate is an important factor in the commercial viability ofthe process. Traditional DLC's typically exhibit very low depositionrates which are insufficient for production of sufficient volumes ofcoated substrates for capacitor manufacturing. Examples of typicaldeposition rates achieved for these feed gases and dielectric types are:approximately 70 Angstroms/min for methane based DLC materials,approximately 500-750 Angstroms/min for tetramethylsilane-based Si-DLCmaterials, approximately 580 Angstroms/min for cyclohexane-based DLCmaterials. The processes and chemistries used in this invention exhibitmuch higher deposition rates, which enable the efficient production ofwound capacitors. For example, a typical deposition rate for the non-DLCdielectric material of the present invention deposited from anoctamethylcyclotetrasiloxane (OMCTS)/oxygen plasma ion beam process canin the range of 10,000 to 20,000 Angstroms/min. Deposition rates rangingbetween about 50 and about 5000 Angstrom/sec, more particularly betweenabout 100 and about 5000 Angstrom/sec, can thus be obtained using theprocess of the invention.

Another embodiment of the invention is applicable in situations wherethe dielectric layer does not adhere well to the substrate. In thissituation, it is desirable to use a first adhesion-promoting layer orinterlayer. Such a layer may utilize different precursor gases ordifferent deposition conditions in order to enhance chemical bonding ofthe dielectric layer to the substrate, or to reduce film stress toenhance adhesion to the substrate. Therefore, the first layer mustadhere well to the substrate and the subsequent and the dielectric layermust adhere well to the first layer. For this situation, a thin (lessthan 500 Angstroms) adhesion promoting layer is typically used with athick (about 1000 Angstroms to about 3 microns) dielectric outer layeron top. A final layer of a different material may also be applied on topof the dielectric to enhance the resistance of the dielectric todegradation due to exposure to air, humidity, or other ambients duringthe storage or processing of the material or assembly or storage of thefinished capacitor.

Examples of suitable organo-silicon compound precursors include silanes,organosiloxanes, or organosilazanes. Examples include:hexamethyldisiloxane, hexamethyldisilizane,tetramethylcyclotetrasiloxane, tetraethoxysilane, andoctamethylcyclotetrasiloxane, tetramethylsilane, and mixtures thereof.Larger organo-silicon molecules such as hexamethyldisiloxane,hexamethyldisilizane, tetramethylcyclotetrasiloxane andoctamethylcyclotetrasiloxane are preferred due to the higher depositionrates that are achieved with these precursors. In a particularembodiment, these silane, siloxane, and silazane precursor gases can bemixed with oxygen and the plasma or ion beam conditions are adjusted toachieve the coating materials of the present invention. However,organo-silicon compounds containing covalently bonded oxygen can beused, which will decrease or eliminate the need for addmixed oxygen.

Typical chemical compositions of the dielectric coatings produced bythis process exhibit significant concentrations of the elements ofcarbon, hydrogen, silicon, and oxygen, and potentially nitrogen. Anexample of composition ranges for dielectrics produced by OMCTS/oxygenchemistries were measured to be in the range of 15-70 atomic % oxygen,more particularly 20-35 atomic % oxygen; 0-40 atomic % hydrogen, moreparticularly 5-30 atomic % hydrogen, even more particularly 20-30 atomic% hydrogen; 0-40 atomic % carbon, more particularly 5-37 atomic %carbon, even more particularly 20-37 atomic % carbon; and 10-35 atomic %silicon, more particularly 15-25 atomic % silicon. A small amount ofargon, i.e. up to 2%, may also be present in the dielectric coating. Thecoatings deposited by this technique are typically completely amorphouswith low pinhole densities and surface roughnesses that match theoriginal substrate. Chemical bonding is also present between the atomsof the coating which differentiates this material from doped material orimplanted or imbedded elements in a base material.

Electrical property measurements of the resulting film show dielectricstrengths generally ranging between about 200 V/μm and about 2400 V/μm.Dielectric strengths greater than about 600 V/μm, more particularlygreater than about 800 V/μm are obtainable. Dissipation factors <2% andmore typically below 1%, are also obtained by the invention.

When rolled capacitors are manufactured using coated metal foils ormetallized polymer films (e.g., films or foils having an exposed metalmargin) produced by the method of the invention, several factors becomeimportant in order to realize high dielectric strengths in workingcapacitors. These factors include the surface roughness of thesubstrate, the metallization thickness of the electrode under thedielectric coating, and the dielectric constant of the gap betweenrolled layers of the dielectric.

The surface roughness becomes important as the dielectric layerthicknesses are decreased below 1 micron. Generally, the roughness mustbe small with respect to the dielectric thickness. As an example, fordielectric coating thicknesses of 0.5 micron, the maximum surfaceroughness (Rmax) should be below about 0.2 micron.

In order to realize the full dielectric strength of these materials,defects in the coating and on the substrate must be electrically“cleared.” Clearing is the isolation of defects by the evaporation ofthe metallized electrode in the vicinity of the defect, usually by highinstantaneous electrical currents. It has been found that, in order toachieve high dielectric strengths, very thin metallization, i.e. lessthan 100 Angstroms, and more preferably, less than 50 Angstroms, must beused as the electrode. This metallization can also be characterized interms of resistivity in units of ohms/square. Preferred metallizationresistivities for this invention, prior to the ion precleaning processwhich removes some metallization, are above about 10 ohms/square, andmore preferably, greater than 20 ohms/square. Optimum metallizationallows the clearing to occur easily, yet allows the remainingmetallization to remain capable of carrying sufficient current forcapacitor charging and discharging. The substrate can be coated on asingle side, or on both sides thereof.

This clearing effect is typically possible only with the use ofmetallized polymer films as the substrates for rolled capacitors sincemetal foils require too much current flow in order to “clear”. Rolledcapacitors of this type require a minimum of two films rolled togetherwith exposed metallization at each “end” of the roll for the twoelectrodes. Additional combinations of layers may be used which comprisesingle-side or double-side metallized polymer films with single-side ordouble-side coatings of dielectrics.

The dielectric constant of the gap between layers is a significantfactor in determining the voltage breakdown characteristics of rolled orparallel plate capacitors. Air exhibits a very low dielectric stress. Asa result, if air is present between the coated metallized film and thetop electrode, the air gap may break down electrically before otherlayers in the material. This breakdown can damage the dielectric that isin close proximity, and cause a short in the capacitor. For this reason,it is well known that many high energy density capacitors areconstructed such that the air in the gap is replaced with oils ofvarious types such as silicone oil or rape seed oil (RSO). The higherdielectric constant of these oils increases the minimum breakdownvoltage of the rolled or parallel plate capacitor. It has been foundthat another viable approach is to eliminate the air gap completely bymetallizing the top surface of the dielectric, as has been done herein,and described in Example A.

The examples which follow illustrate the superior performance of themethod of this invention and the products produced thereby. The examplesare for illustrative purposes only and are not meant to limit the scopeof the claims in any way.

EXAMPLE A

In this example, several samples of silicon wafer, capacitor-gradealuminum foil, and aluminized silicon wafers (wafer segments onto whicha thin layer of aluminum was evaporated) were mounted into a vacuumdeposition system. The vacuum chamber was then evacuated to a pressureless than 5×10⁻³ Torr. The substrates were pre-cleaned using an argonion beam generated from a Hall-current closed-drift ion source of thetype disclosed in U.S. Pat. No. 5,973,447, the entire contents of whichare incorporated herein by reference (DIAMONEX “CD SOURCE”) with anominal 3.5-inch diameter anode channel at a throw distance ofapproximately 7 inches. The beam conditions for the argon pre-clean were40 sccm argon flow, 1-minute etch with no sample motion, 8 amps of anodecurrent, and 90 V anode-to-ground voltage. An interlayer was thendeposited which consisted of 25 sccm of tetramethylsilane (TMS) injectedinto the argon plasma of the CD SOURCE for one minute at 8 A anodecurrent and 60 V anode-to-ground voltage. The dielectric layer was thendeposited using octamethylcyclotetrasiloxane (OMCTS) and oxygen. Theflow rate of OMCTS was the equivalent of 10 g/hr of water, oxygen flowrate through the ion source was 20 sccm, and 30 sccm of argon was usedin the ion source, and the beam conditions were 6 A anode current and 60V anode-to-ground voltage. The deposition lasted 1.5 minutes.

The resulting dielectric coating was measured to be 0.473 micron thick,resulting in a static deposition rate of 0.315 micron/minute or 50Angstroms/second.

The electrical characteristics of the composite coating were measured byevaporating small “dots” of known area of aluminum metallization whichacted as a top electrode. The metallization under the dielectric actedas the “bottom electrode”. Increasing voltage was applied across the topand bottom electrodes and the current flow and capacitance was measured.The electrical characteristics were as follows:

-   Breakdown volts (aluminum foil samples): 303V average-   Dielectric strength (Al foil): 640 V/micron-   Dissipation factor (Al foil, average): 3.5×10⁻³-   Coating resistivity (Al foil, average): 7.76×10¹⁵ ohm-cm-   Dielectric constant (Al foil, average): 2.38

EXAMPLE B

In this example, several samples of silicon wafer, capacitor-gradealuminum foil, and aluminized silicon wafers (wafer segments onto whicha thin layer of aluminum was evaporated) were mounted into a vacuumdeposition system. The vacuum chamber was then evacuated to a pressureless than 5'10⁻³ Torr. The substrates were pre-cleaned using an argonion beam and a 3.5-inch CD SOURCE as described in Example A at a throwdistance of approximately 7 inches. The beam conditions for the argonpre-clean were 40 sccm argon flow, 1-minute etch with no sample motion,8 amps of anode current, and 90 V anode-to-ground voltage. An interlayerwas then deposited which consisted of 25 sccm of TMS injected into theargon plasma of the CD SOURCE for one minute at 8 A anode current and 60V anode-to-ground voltage. The dielectric layer was then deposited usingOMCTS and oxygen. The flow rate of OMCTS was the equivalent of 5 g/hr ofwater, oxygen flow rate through the ion source was 200 sccm, 30 sccm orargon were used in the ion source, and the beam conditions were 6 Aanode current and 100 V anode-to-ground voltage. The deposition lasted1.0 minutes. The resulting dielectric coating was measured to be 0.595micron thick, resulting in a static deposition rate of 0.595 micron/minor 100 Angstroms/second.

The electrical characteristics of the composite coating were measured asfollows:

-   Breakdown volts (aluminum foil samples): 316V average-   Dielectric strength (Al foil): 531 V/micron-   Dissipation factor (Al foil, average): 5.1×10⁻³-   Coating resistivity (Al foil, average): 5.00×10¹⁵ ohm-cm-   Dielectric constant (Al foil, average): 4.83    The conditions of example B were repeated except that the    anode-to-ground voltage was set to 120 Volts. The chemical    composition of the resulting dielectric coating was measured to be    carbon: 23.5 atomic %, hydrogen: 22.0 atomic %, oxygen: 34.4 atomic    %, silicon: 20.0 atomic %, argon: 0.10 atomic %. The surface    morphology of this sample was analyzed by Atomic Force Microscopy    (AFM) which showed the coating to be totally amorphous without    pinholes, and with a surface roughness (Ra) of 250 Angstroms.    Analysis of this sample by infrared spectroscopy showed evidence of    a variety of chemical bonds including Si—O, O—Si—O, C—H, C—C, and    C═C in the dielectric material.

EXAMPLE C

In this example, a roll of aluminum-metallized Q83 25-micron thickpolymer film with resistivity of <1 ohm-square was mounted in a vacuumweb-handling system (WHS, CHA Mark 50). The web was fed through tensionrollers and around a water-cooled drum and then to a take-up spool. Thevacuum chamber was then evacuated to a pressure less than 5×10⁻³ Torr.The film material was moved in front of the ion source once for an ionpreclean process using an argon ion beam and a 3.5-inch CD SOURCE at athrow distance of approximately 7 inches. The beam conditions for theargon preclean pass were 40 sccm argon flow, 6 amps of anode current,and 80 V anode-to-ground voltage. The drum speed was set to 2.0 feet perminute (fpm). No interlayer was used prior to the deposition of thedielectric layer. The dielectric layer was then deposited on the reversepass of the web-handling system using OMCTS and oxygen. The flow rate ofOMCTS was 0.1 g/min equivalent of tetraethoxysilane (TEOS), oxygen flowrate through the ion source was 30 sccm, and 20 sccm argon were used inthe ion source, and the beam conditions were 6 A anode current and 90 Vanode-to-ground voltage. A total of 25 feet of dielectric material wasdeposited onto the polymer film during a continuous coating pass. Thedrum speed for the dielectric deposition step was set to 0.1 fpm. Theresulting dielectric coating thickness was estimated to be about 1micron, based on previous similar deposition runs.

The electrical characteristics of the composite coating were measured asfollows:

-   Breakdown volts: 293V average-   Dielectric strength: 262 V/micron-   Dissipation factor: 4.7×10⁻³-   Coating resistivity: 2.93×10¹⁵ ohm-cm-   Dielectric constant: 3.86    The dielectric deposition conditions of example C were repeated in    another experiment in which an interlayer was used to improve    adhesion to the substrate. The chemical composition of the    dielectric layer was measured to be carbon: 26.5 atomic %, hydrogen:    25.0 atomic %, oxygen: 29.0 atomic %, silicon: 19.5 atomic %.

It was determined that the measured dielectric strength of this materialwas decreased due to the surface roughness of the material and therelative thickness of the aluminum metallization on the Q83 polymerfilm.

EXAMPLE D

In this example, a roll of aluminum-metallized 12-micron thick polyesterpolymer film with metallization resistivity of 3 ohm-square thick, wasmounted in the vacuum web-handling system of Example C. The chamber wasthen evacuated and the polyester film was argon ion beam precleaned, anda dielectric layer was deposited according to Example C, with the onlydifference being that the anode-to-ground voltage was 92 Volts. A totalof 30 feet of polyester film was coated with the dielectric materialduring a continuous coating pass. The resulting dielectric coatingthickness was estimated to be about 1 micron thick based on previoussimilar deposition runs.

The breakdown voltage and dielectric strength were evaluated using asingle copper electrode (1.5 square inches area) that was placed on topof the dielectric. A high voltage power supply was attached to thiscopper block and also to an un-coated margin on the film material, whichleft a portion of the aluminum metallization exposed. The power supplyvoltage was then increased and the current was monitored. Resistors inseries with the copper block limited the current to 1.0 mA in the eventof a dielectric failure.

FIG. 1 shows the data obtained for multiple points on the samplesurface. Clearing events are typically seen as current spikes at aparticular voltage. The subsequent drop in current indicates that adefect or void in the coating was evaporated away as a result of thecurrent flow and that the bulk of the dielectric material surfaceremained intact. After clearing events in the 200-350V range, thedielectric coating was able to withstand up to 800V without current flowindicating a dielectric strength of at least 727 V/micron. The chemicalcomposition of the deposited dielectric material was measured byRutherford Backscattering and Hydrogen Forward Scattering Spectrometryand was verified to be the same before and after the breakdown test.

EXAMPLE E

In this example, a roll of aluminum-metallized 6-micron thick polyesterpolymer film with resistivity of 22 ohm-square was mounted in the vacuumweb-handling system of Example C. The chamber was then evacuated and thepolyester film was argon ion beam precleaned at a drum speed of 0.5 fpm.An interlayer was deposited prior to the deposition of the maindielectric layer. The deposition condition for the interlayer were 40sccm Ar, 6 amp of anode current, and 60 V anode-to-ground voltage, thedrum speed of 4 fps and the flow rate of OMCTS to be 0.1 g/min. Thedielectric layer was deposited under the same conditions as in ExampleC, except the drum speed was 0.2 fpm. The resulting dielectric coatingthickness was estimated to be about 0.5 micron based on previous similardeposition runs.

The breakdown voltage and dielectric strength were evaluated using a6-micron thick PET film with 22 ohms/square of Al metal as the topelectrode. A 12 mm-diameter of 25 micron thick polyester film mask wasplaced between the clearable top electrode and the dielectric film Ahigh voltage power supply was attached to the 22 ohms/square Al topelectrode and also to an uncoated margin on the film material which lefta portion of the aluminum metallization exposed. The power supplyvoltage was then increased and the current and capacitance weremonitored. As the electrical field increased, electrostatic forces weregenerated which resulted in excellent contact between the top electrodeand the dielectric film. As illustrated in FIG. 2, after clearing eventsin the 650 V range, the capacitance dropped indicating that thedielectric strength of the coating was 1300 Volts per micron.

EXAMPLE F

A dielectric coating material on a roll of aluminum-metallized 6-micronthick polyester polymer film was prepared by the same procedure as inExample E, and tested for dielectric strength. In order to eliminate theair gap between the top electrode and the dielectric film, a drop ofcapacitor grade rapeseed oil was applied. As illustrated in FIG. 3,after clearing events in the 750 V range, the measured capacitancedropped indicating the dielectric strength of the dielectric coating was1500 volts/micron. Compared to the test in Example E, the replacement ofair in the gap between the top electrode and the dielectric film with ahigher dielectric constant material, such as an oil, resulted in higherbreakdown strength value. The addition of capacitor grade oil is acommon practice for packaged wound capacitors. This Example alsodemonstrated that the dielectric films produced by this invention arestable with rapeseed oil (RSO). In addition, the dielectric material isstable in other capacitor oils such as silicone oil.

Similar processes were used to produce coatings on metallized webshaving C: 35±2 atomic %, H: 25±1 atomic %, O: 22±2 atomic %, and Si:15±1 atomic %.

Without departing from the spirit and scope of this invention, one ofordinary skill in the art can make various changes and modifications tothe invention to adapt it to various usages and conditions. As such,these changes and modifications are properly, equitably, and intended tobe, within the full range of equivalents of the claims.

1.-12. (canceled)
 13. A dielectric-coated substrate, comprising a firstlayer of dielectric coating material comprising carbon, hydrogen,silicon, and oxygen and having a dielectric strength ranging from about200 V/μm to about 2400 V/μm.
 14. The dielectric-coated substrate ofclaim 13, wherein the dielectric coating material layer has a dielectricstrength ranging from about 600 V/μm to about 2400 V/μm.
 15. Thedielectric-coated substrate of claim 13, wherein the dielectric coatingmaterial layer has a dissipation factor less than about 2%.
 16. Thedielectric-coated substrate of claim 13, wherein the substrate comprisesa film or foil having an exposed metallic margin.
 17. Thedielectric-coated substrate of claim 16, wherein the substrate is coatedon two sides thereof.
 18. The dielectric-coated substrate of claim 13,further comprising a second dielectric coating material layer disposedadjacent to the first layer.
 19. A capacitor comprising thedielectric-coated substrate of claim 13.